I. Field of the Invention
This invention relates to the preparation of hydrazine compounds and specifically to the preparation of anazine or of a mixture of an azine and a hydrazone by reacting hydrogen peroxide with ammonia or with a mixture of ammonia and a primary or secondary amine in the presence of a carbonyl compound and a catalyst containing selenium.
II. Description of the Prior Art
It is known that the oxidation of carbonyl compounds, aldehydes and ketones in the presence of ammonia by mineral peroxide compounds leads to various compounds according to the nature of the peroxide compound and the conditions of operation. Thus the reaction between ammonia, an aldehyde or a ketone, and hydrogen peroxide leads to amino peroxides (see, for example, J. Chem. Soc. (c) 1969, page 2663) or to oximes in the presence of tungstic or molybdic acids (see, for example, J. Gen. Chem. U.S.S.R. 1960, 30, 1635).
It is also known that primary or secondary amines are easily oxidized by various peroxide compounds into widely differing oxygenated products such as the hydroxylamines, nitroso or nitro derivatives, oximes, compounds possessing azoxy structures, amides, etc., according to the particular structure of the reagents or the conditions of the reaction. For example, the oxidation of the aliphatic primary amines into nitroalkanes with peracetic acid (J. Am. Chem. Soc. 79, 5528, 1957) or other percarboxylic acids (see, for example, H.O. Larson in "The Chemistry of the Nitro and Nitroso Groups," part I, page 303, published by H. Feuer, Interscience, New York, 1969) has been described.
The aromatic primary amines have been oxidized into corresponding nitroso, nitro, or azoxy derivatives by pure percarboxylic acids or by a mixture of acetic acid and 30% aqueous solution of hydrogen peroxide (J. Am. Chem. Soc. 82 3454 (1960); see also W.H. Weaver in "The chemistry of the Nitro and Nitroso Groups" Part 2, page 29, published by H. Feuer, Interscience New York, 1970). Aniline has also been oxidized into azoxybenzene by hydrogen peroxide in the presence of acetonitrile (J. Org. Chem. 26, 659 (1961)).
In the previous patents and applications for patents the assignee of this application has moreover described new processes for the synthesis of azines (I) by oxidation of ammonia in the presence of a carbonyl compound (IV) with one of the peroxide compound mentioned above, in accordance with the general reaction ##EQU5##
The oxidation can be carried out with a percarboxylic acid (pending U.S. application Ser. No. 290,507, filed Sept. 20, 1972), a diacyl peroxide (pending U.S. application Ser. No. 308,836, filed Nov. 22, 1972), hydrogen peroxide in the presence of salts as catalysts (pending U.S. application Ser. No. 267,921, filed June 30, 1972), hydrogen peroxide in the presence of nitriles as co-reactants (French Pat. No. 2,092,734, 734, applied for June 12, 1970, and pending U.S. application Ser. No. 152,413, filed June 11, 1971), hydrogen peroxide in the presence of esters as co-reactants (pending U.S. application Ser. No. 340,763, filed Mar. 13, 1973), a hydrogen peroxide in the presence of amides or imides as co-reactants (pending U.S. application Ser. No. 341,057, filed Mar. 14, 1973), and hydrogen peroxide in the presence of cyanogen compounds as co-reactants (pending U.S. application Ser. No. 340,762, filed Mar. 13, 1973).
The applications have also described the synthesis of hydrazones (II) by the joint oxidation of a primary or secondary amine (III) and ammonia in the presence of a carbonyl compound (IV) with a percarboxylic acid, a diacyl peroxide, or hydrogen peroxide in the presence of salts or bases as catalysts or in the presence of co-reagents such as nitriles, esters, amides, imides, or cyanogen compounds (pending U.S. application Ser. No. 406,467 filed Oct. 15, 1973) in accordance with the general reaction ##EQU6##